Solid acid catalyst

Details Solid acid catalyst Solid acid catalyst

2000-06-19

2002-05-07

Bell, Mark L. (Department: 1755)

Catalyst, solid sorbent, or support therefor: product or process

Catalyst or precursor therefor

Organic compound containing

C502S208000, C502S213000, C502S327000, C502S355000, C554S162000, C568S618000

Reexamination Certificate

active

06383970

ABSTRACT:

TECHNICAL FIELD
The present invention relates to a solid acid catalyst and to a method for producing an ester, a ketal or an acetal by using the solid acid catalyst.
PRIOR ART AND PROBLEMS TO BE SOLVED BY THE INVENTION
A solid acid catalyst has an advantage such as an easy operation for isolating a product after the reaction. Therefore, it is has been examined from the viewpoint of ability for use in various organic reactions. For example, there are known a zeolite (JP-A 61-200943), a silicate of the IV group elements (EP0623581A2), hydrous zirconium oxide (JP-B 4-28250) and the like for producing an ester and, then, an organic solid catalyst such as an ion-exchange resin and an inorganic solid catalyst such as hydrous zirconium oxide (JP-A 63-146838) and mordenite (JP-A 60-188338) for producing an acetal or a ketal. Those described in U.S. Pat. No. 4,202,798 and U.S. Pat. No. 4,251,350 are known.
In case a solid catalysts selected therefrom are used especially in a liquid phase reaction, the activity or the durability of the strength of formed catalyst can not satisfy, because of insufficient activity at a low temperature, elution of a catalytic component into the liquid phase, and the like.
It is an object of the present invention to provide a solid acid catalyst which develops its high activity and exhibits its high durability in various organic reactions.
DISCLOSURE OF THE INVENTION
The present invention relates to a solid acid catalyst having the following structure (A), structure (B) and metal atom (C) and to a method for producing an ester, a ketal or an acetal by using the solid acid catalyst.
Structure (A): a structure in which a hydrogen atom is eliminated from at least one of OH groups contained in an inorganic phosphorus acid;
Structure (B): a structure in which a hydrogen atom is eliminated from at least one of OH groups contained in an organic phosphorus acid represented by the formula (1) or (2);
wherein each of —R
1
and —R
2
is selected from —R, —OR, —OH and —H in which at least one of —R
1
and —R
2
is —R or —OR, given that —R is an organic group having 1 to 22 carbon atoms;
Metal atom (C): at least one atom selected from aluminum, gallium and iron.
In this description, the structure (A) is derived from a phosphorus-containing compound (phosphorus acid) such as phosphonic acid, phosphorous acid, phosphinic acid, phosphoric acid, orthophosphoric acid and metaphosphoric acid, and other isomers or derivatives thereof. The phosphorus acid may be an oxy acid of phosphorus.
Further, the present invention provides the solid acid catalyst as mentioned above, wherein the structure (A) is a structure derived from orthophosphoric acid.
Furthermore, the present invention provides the solid acid catalyst as mentioned above, wherein the structure (B) is a structure derived from phosphonic acid.
Then, the present invention provides a method for producing an ester, which comprises producing an ester from a raw ester or raw carboxylic acid (a) and a raw alcohol (b) by using the catalyst as defined above.
The present invention provides also a method for producing a ketal or an acetal, which comprises producing a ketal or an acetal from a ketone or aldehyde (c) and an alcohol (d) by using the catalyst as defined above.
The present invention provides a method for preparing a solid acid catalyst having the following structure (A), structure (B) and metal atom(C);
Structure (A): a structure in which a hydrogen atom is eliminated from at least one of OH groups contained in an inorganic phosphorus acid;
Structure (B): a structure in which a hydrogen atom is eliminated from at least one of OH groups contained in an organic phosphorus acid represented by the formula (1) or (2):
wherein each of —R
1
and —R
2
is selected from —R, —OR, —OH and —H in which at least one of —R
1
and —R
2
is —R or —OR, given that —R is an organic group having 1 to 22 carbon atoms;
Metal atom (C): at least one atom selected from aluminum, gallium and iron.
The present invention provides use of the catalyst as defined above for production of an ester compound.
The present invention provides use of the catalyst as defined above for production of a ketal compound or an acetal compound.
The catalyst of the invention may be that being obtainable from the inorganic phosphorus-containing compound for the structure (A), the organic phosphorus acid for the structure (B) and a metal compound for the metal (C).
MODES FOR CARRYING OUT THE INVENTION
In the structure (A) in the solid acid catalyst of the present invention, the inorganic phosphorus acid includes orthophosphoric acid, metaphosphoric acid and a condensed phosphoric acid such as pyrophosphoric acid. Orthophosphoric acid is preferable from the viewpoint of performance.
Also, in the structure (B), the organic phosphorus acid represented by the formula (1) or (2) includes phosphonic acid, phosphonic acid monoester, phosphinic acid, phosphoric acid monoester, phosphoric acid diester, phosphorous acid monoester and phosphorous acid diester. A mixture thereof may be included. Phosphonic acid is preferable.
The organic group —R in the organic phosphorus acid is preferable to be an alkyl group such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-hexyl, 2-ethylhexyl, octyl, dodecyl and octadecyl or to be an aryl group such as phenyl and 3-methylphenyl. Also, one of these groups may be combined with an amino group, an alkoxy group, a carbonyl group, an alkoxycarbonyl group, a carboxyl group, a halogen group including chloro group, phosphono group, sulfo group or the like for use.
The metal atom (C) is preferably aluminum from the viewpoint of performance and/or cost. Then, it may contain a small amount of a metal atom other than aluminum, gallium and iron in order to improve selectivity or other performances.
From the viewpoint of performance, the ratio of the structure (A) to the structure (B) in the solid acid catalyst of the present invention is preferable in such ratio that the molecular ratio x of an organic phosphorus acid represented by the following formula (3) is 0.01 to 0.99. Here, [Pinorg] shows the molecular number of phosphorus atom contained in the structure (A) and [Porg] shows the molecular number of phosphorus atom contained in the structure (B).
x
=[Porg]/([Pinorg]+[Porg])  (3)
Then, a more preferable ratio is present in the ratio x depending upon a reaction to be utilized. The x is preferably 0.01 to 0.7 and more preferably 0.01 to 0.5 at the production of an ester. On the other hand, the x is preferably 0.05 to 0.99 and more preferably 0.1 to 0.8 at the production of a ketal or acetal.
Then, the value Y represented by the following formula (4) is preferably 0.15 to 2.0.
Y
=[Metal]/([Pinorg]+[Porg])  (4)
Here, [Metal] shows the number of the metal atoms (C) in the catalyst.
All of the metal atom (C) contained in the catalyst doesn't bond necessarily to the structure (A) or (B). Some of the metal atom (C) may be present in the form of a metal oxide, metal hydroxide or the like.
As the method for preparing the solid acid catalyst of the present invention, a precipitating method, a method for impregnating an inorganic phosphorus acid and an organic phosphorus acid onto a metal oxide or a metal hydroxide, and a method for substituting an inorganic phosphorus acid group in an inorganic phosphorus acid aluminum salt-gel for an organic phosphorus acid group or the like is used. The precipitating method is preferable. Then, the method for preparing the solid acid catalyst may comprise merely mixing a powder of an inorganic phosphorus acid salt with another powder of an organic phosphorus acid salt, as it is, homogeneously. Here, the powder of the inorganic phosphorus acid salt may comprise the above-mentioned structure (A) and the metal atom (C), and the other powder of the organic phosphorus acid salt may comprise the above-mentioned structure (B) and the metal atom (C). In the precipita

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